Mixed Ligand Coordination Polymers for Metallogelation and Iodine

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Mixed Ligand Coordination Polymers for Metallogelation and Iodine Adsorption Parthasarathi Dastidar, and Swapneswar Mondal Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01547 • Publication Date (Web): 04 Dec 2018 Downloaded from http://pubs.acs.org on December 5, 2018

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Crystal Growth & Design

Mixed Ligand Coordination Polymers for Metallogelation and Iodine Adsorption Swapneswar Mondal and Parthasarathi Dastidar* School of Chemical Sciences, Indian Association for the Cultivation of Science (IACS), 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata – 700032, West Bengal, India Coordination Polymers, Metallogels, Crystal Engineering, Supramolecular Gels, Nanoparticles, Iodine Adsorption ABSTRACT: A bis-pyridyl-bis-amide derivative of diphenyl methane (L1) and terephthalate (TA) were combined with a number of metal salts [Cu(II), Zn(II), Ni(II), Co(II) and Cd(II)] in 1:1:1 molar ratio to generate a series of coordination polymers (CP1A-CP5) which were thoroughly characterized by single crystal X-ray diffraction. All the CPs turned out to be lattice occluded crystalline solid having 4x4 grid framework structures. Under suitable conditions, the reactants of the corresponding CPs produced metallogels as envisaged considering a crystal engineering based structural rationale. One of the CPs, namely CP5 demonstrated the ability to adsorb molecular iodine both in vapor and solution phase. Iodine adsorption was also found to be reversible as evident from its release in ethanol from both CP5@I2 (vapor) and CP5@I2(solution). In situ synthesis of silver nanoparticles was also achieved in the gel matrix of L1 without the help of any exogenous reducing agent.

Introduction. There have been increased research interests in developing rational approaches to design supramolecular gels1-6 as they offer potential applications in various areas of material science.7-12 Supramolecular gels are visco-elastic materials that comprise a small amount of gelator(s) and a large volume of solvent(s). Within a gel network formed due to supramolecular assembly of the gelator molecules (known as selfassembled fibrilar networks or SAFiNs13) the solvent molecules are immobilized due to surface tension or capillary force action resulting in a solid like materials called gels. Various non-covalent (supramolecular) interactions such as hydrogen bonding, halogen bonding, - stacking, van der Waals interactions, charge transfer interactions etc. are responsible for the formation of SAFiNs. Metallogels14-16 are supramolecular gels wherein metal-ligand coordination along with other supramolecular interactions takes part in SAFiNs. Coordination polymers (CPs),17,18,19 coordination 20-22 complexes (CCs), cross-linked coordination polymers23 are reported to form metallogels. Gels containing metal nanoparticles also belong to this class.24-26 Gels are believed to be formed due to frustrated or failed crystallization process wherein a solution containing gelator molecules, under suitable conditions, takes a kinetically driven path towards meta-stable gels instead of thermodynamically stable crystals. In the absence of detail molecular level information of gelation mechanism, it is understandable that designing gelator molecule a priori is indeed a difficult task. Nevertheless, there have been efforts by various groups towards meeting this goal.27-30 Our group has successfully

demonstrated the link between gels and crystal engineering31, and generated a large number of gels displaying intriguing functions by exploiting the merit of supramolecular synthons in the context of crystal engineering.32,33 However, this approach is particularly valid for organogels wherein the solvent is organic and consequently do not participate in gel network formation. Metallogels, on the other hand, are usually formed in aqueous solvents and in here, water being good hydrogen bond donor as well as acceptor, do participate in gel network formation. This is quite evident from the crystal structure analysis of a number of hydrogelators.34-36 We37,38 and others,39 therefore, proposed that compounds prone to form lattice occluded crystalline solids (LOCS) are potential target as gelators since in both LOCS and gel, a large number of solvent molecules are entrapped. Following this hypothesis, we have designed a number of metallogels that displayed intriguing functions.17 Iodine plays crucial role in the area of functional materials, biomedical applications, environmental chemistry etc.40,41 For examples, applications of iodine and its isotopes are found in cancer treatment, and electrical conductivity.42,43 Iodine isotopes pose an environmental hazard in nuclear affluent.44-48 Therefore, demand for materials capable of adsorbing iodine has gained increased interest. Chalcogenide aerogels,49 functionalized clays, and silver-based porous zeolitic materials50,51 for iodine adsorption have been studied extensively. However, limited adsorption ability, high cost and environmental issues with these materials created demand for developing alternative materials. Coordination compounds such as CPs possess ability to adsorb iodine not only in its pore (for porous CPs) but

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also the framework of CPs facilitates iodine adsorption through non-covalent interactions involving iodine and various sorption sites such as -conjugated moiety, pyridyl, hydroxyl, ether, amino functionalities (encouraging halogen bonding) etc.52-61 With this background, we, set out to synthesize a series of CPs by reacting a bis-pyridyl-bis-amide ligand having diphenylmethane backbone (L1), terephthalate (TA) and various metal ions [Cu(II), Zn(II), Ni(II), Co(II) and Cd(II)] in 1:1:1 molar ratio. While the expected 4x4 grid framework structure having hydrogen bond capable amide backbone of L1 in the CPs is expected to occlude solvent molecules in its crystal lattice thereby forming LOCS, the aromatic  backbone of both the ligands (L1 and TA) might help adsorb iodine. Therefore, the resulting CPs are expected to form metallogels under suitable conditions and also the CPs might have ability to adsorb iodine. We report the solvothermal synthesis of a series of CPs (CP1A-CP5) derived from L1, TA and the metal salts in DMF/methanol/water and their thorough characterization by single crystal X-ray diffraction (SXRD) (Scheme 1). All the CPs turned out to be LOCS as envisaged. Except the CP derived from Cu(II), all the other CPs displayed ability to form metallogel (MG1, MG2, MG4 and MG5) in DMF/water (1:1 v/v) at room temperature. The Co(II) CP i.e. CP5 displayed the ability to adsorb iodine both from solution as well as from vapor. Iodine adsorption by CP5 was found to be reversible.

Scheme 1. Schematic representation of the synthesis of CPs and metallogels Results and Discussions. Single crystals of the CPs obtained by solvothermal crystallization were subjected to SXRD (Table 1, see experimental section). Crystal structures of CP1A and CP1B. The coordination polymers CP1A and CP1B were pseudopolymorphs because CP1A crystallized in the triclinic space group P-1 whereas CP1B displayed the orthorhombic space group Pbca and the lattice occluded solvents were different in these cases; while CP1A contained three water and one MeOH (disordered around a center of inversion) as lattice occluded solvates, CP1B contained only one MeOH in the corresponding

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asymmetric unit. The metal center in CP1A displayed a slightly distorted octahedral geometry wherein the axial sites were coordinated by two pyridyl N atoms of L1 and the equatorial positions were occupied by O atoms of two TA (unidentate coordination mode) and two water molecules. On the other hand, Cd(II) in CP1B displayed pentagonal bipyramidal geometry; in here, the equatorial sites were occupied by O atoms of two TA (bidentate coordination mode) and one water molecule. The relative orientation of the terminal pyridyl N atoms in both the structures was syn whereas that of the amide carbonyl O atoms exhibited anti for CP1A and syn for CP1B. Both the ligands (L1 and TA) were involved in extended coordination with Cd(II) metal center resulting in 2D grid network in both the structures; the grid architecture was corrugated 2D sheets for CP1A and 2D layered network for CP1B. The 2D networks were packed in parallel fashion in both the cases. Except the disordered MeOH, all the solvates (water) in CP1A were found to be stabilized in the crystal lattice by hydrogen bonding interactions involving the amide backbone of L1, metal bound water and themselves. In CP1B, on the other hand, the solvate MeOH was found to be tightly held in the crystal lattice through hydrogen bonding interactions involving amide functionality of L1 (Figure 1 and 4).

Figure 1. Crystal structure illustrations of CP1A and CP1B along with their corresponding network topology62,63

Crystal structures of CP2A and CP2B. Like CP1A/CP1B, these two CPs were also pseudopolymorph as evident from their different space group (monoclinic C2/c for CP2A and P-1 for CP2B) and different lattice occluded solvate content (3H2O+MeOH for CP1A and 4H2O+MeOH for CP2B). The Ni(II) metal center in CP2A was located on a center of inversion thereby displaying perfect octahedral coordination environment; the axial positions were occupied by water molecules whereas the equatorial sites were coordinated by two O atoms of TA (unidentate coordination mode) and two N atoms of pyridyl moiety of L1. On the other hand, the metal center in CP2B showed slightly distorted octahedral geometry displaying identical coordination environment of CP2A.


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The ligand L1 adopted anti-anti and anti-syn conformation for CP2A and CP2B, respectively. The coordination network structures in both cases may best be described as 2D sheet that were packed in parallel fashion. The lattice occluded solvent molecules were found tightly held in the lattice via hydrogen bonding interactions with the amide backbone of the ligand L1 (Figure 2 and 4).

experimental patterns obtained from bulk crystals (Figure S13-19, supporting information) . Moreover, thermogravimetric analysis strongly supported the solvent content as observed in SXRD analysis (Figure S2026, supporting information). Thus, isolation and characterization of these CPs clearly established that the network structures were 2D and the hydrogen bond capable backbone (amide) of L1 played a crucial role in stabilizing the lattice occluded solvents through hydrogen bonding interactions as envisaged (Figure 4).

Figure 2: Crystal structure illustrations of CP2A and CP2B along with their corresponding network topology62,63

Crystal structures of CP3, CP4 and CP5. These CPs along with CP2B having identical space group (triclinic, P-1) and near identical cell dimensions (see Table 1) were isomorphous and therefore, they displayed identical crystal packing. The corresponding metal centers Cu(II), Zn(II) and Co(II) for CP3, CP4 and CP5, respectively being located on a general position displayed slightly distorted octahedral geometry wherein the axial positions were occupied by water molecules and the equatorial sites were coordinated by two N atoms of L1 and two O atoms of TA (unidentate coordination mode). The ligand L1 adopted anti-syn configuration in all the cases as also observed in CP2B. The coordination networks were 2D sheet in all these structures. As expected, the lattice occluded solvents (3H2O, 3H2O+MeOH and H2O+MeOH for CP3, CP4 and CP5, respectively) were found to be involved in hydrogen bonding with the amide backbone of the ligand L1 (Figure 3 and 4).

Figure 3. Crystal structure illustrations of CP4 and the corresponding network topology62,63; CP3 and CP5 (being isomorphous to CP4) are not shown.

It may be mentioned that the crystalline phase purity of all the crystals was reasonably high as the simulated powder diffraction patterns matched well with that of the

Figure 4. Illustration of crystal packing of all the CPs displaying lattice occluded solvents (color code: H2O – orange in CP2A, CP2B, CP3 and CP4; H2O – yellow in CP1A and CP5; MeOH – magenta)

Metallogelation. The foregoing discussions on the crystal structures of the CPs clearly indicated that it was worthwhile to explore metallogelation with the reactants of the CPs i.e. L1, TA and the corresponding metal salts. Before exploring metallogelation, we first studied the gelation properties of L1. It turned out that L1 was an excellent gelator of DMSO/water (3:2 v/v) with a minimum gelator concentration of 4 wt %. Guided by the crystal structures of the CPs, we reacted L1, TA and the corresponding metal salt in 1:1:1 molar ratio in DMF/water (1:1 v/v) that produced metallogels instantaneously after 5-10 minutes of sonication under ambient conditions except for Cu(NO3)2 as evident from tube inversion test (Table 2, Scheme 1, see experimental section). Rheology. More conclusive data were obtained when these metallogels were subjected to dynamic rheology (Figure 5). Gel being visco-elastic material is expected to display non Newtonian behavior in rheological studies. Frequency sweep plot wherein elastic modulus (Gˊ) and viscous or loss modulus (Gˊˊ) are plotted against the frequency ( rad/s) should typically display the following behavior for a gel sample: (a) Gˊ must be much larger than Gˊˊ and (b) Gˊ should be frequency invariant throughout the entire frequency range. Frequency sweep data for the aqueous gel of L1 and all the metallogels carried out at a fixed strain of 0.1 % (suggested by amplitude sweep experiments, Figure S31) displayed the characteristic signature of visco-elastic materials



confirming that they were indeed gels. Tan  (Gˊˊ/ Gˊ) values for all the gels were greater than 0.1 (Tan  0.230.42) indicating that the gels were significantly strong. The average Gˊs in the linear visco-elastic region were within the range of ~2-237 kPa (Table 2).

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CPs.65,66 In solution phase, CP5 (10 mg) was kept immersed in I2 solution in pet ether (3 mL, 5 mmol) in a closed container for 1 day. Once again visual observation (turning dark pink I2 solution to light pink) was indicative of I2 adsorption. The I2 adsorbed solid CP5@I2(solution) was then filtered and washed several times with pet ether to remove adhered I2. TGA data indicated that 30.3 wt % adsorption of I2 by CP5 was achieved in solution phase. The value attributed to ~0.9 molecule of I2 adsorbed per formulae unit of CP5. The data were found consistent with that displayed by quite a few CPs.65-68 (Figure 7)

Figure 5. Frequency sweep plot for all the gels

Microscopy. To visualize the morphology of the gel network, we carried out TEM imaging of the dried gels (see experimental section). Several micrometer long plate like morphology was observed in the TEM images in dried gels of L1, MG1 and MG4. Selected area electron diffraction (SAED) of the microplates observed under TEM did not show any diffraction confirming that they were not microcrystals precipitated out during TEM sample preparation. Although highly entangled fibrilar morphology is typical for supramolecular gels, such tape type of morphology as observed here is not uncommon (Figure 6).64 It may be noted that TEM images of MG2 and MG5 could not be recorded due to the possible magnetic properties arising because of Ni(II) and Co(II) in the metallogel.

Figure 7. visual observation of I2 adsorption and TGA profile of I2 release.

FT-IR spectrum of CP5, CP5@I2(vapor) and CP5@I2(solution) were compared; the spectra were nearly superimposable suggesting weak interactions of I2 with CP5. PXRD patterns of as synthesized CP5, CP5@I2(vapor) and CP5@I2(solution) were also compared; all the patterns were in good agreement indicating no phase change due to I2 adsorption which further supported physical adsorption of I2 through weak interactions (Figure 8).

Figure 6. TEM images of the gels (inset – SAED).

Iodine adsorption and release. All the CPs were subjected to I2 adsorption both in vapor phase and in solution. Except CP5, all the CPs failed to show any I2 adsorption ability in both the phases as evident from visual observation. In a typical experiment in vapor phase, CP5 (10 mg) was subjected to I2 vapor in a closed container for 1 day at room temperature. Brown solid CP5 turned dark pink (nearly black in naked eyes) solid CP5@I2(vapor) which was thoroughly washed with pet ether to remove excess I2 adhered to the surface of the powdered sample of CP5. The amount of I2 adsorbed by CP5 was quantified by thermogravimetric analysis (TGA) that showed 21.4 wt % adsorption. Thus, per formulae unit of CP5 was able to adsorb ~0.6 molecules of I2. The data were comparable to that observed for many reported

Figure 8. FT-IR and PXRD of CP5 under various conditions.

Release of I2 from the iodine adsorbed CP5 (both phases) was easy and spontaneous in polar organic solvents like EtOH. For this purpose, 1 mg of CP5@I2(vapor)/ CP5@I2(solution) was immersed in 3 mL of EtOH. Colorless EtOH layer gradually turned brown within 4 h. In situ UV-vis absorption showed linear increase of the absorbance at 220-400 nm suggesting steady release of I2 from iodine adsorbed CP5 (Figures S32-33, supporting information) Synthesis of Ag nanoparticles within the gel matrix of L1.


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We also considered exploring the possibility of generating metal nanoparticles (MNPs) in the gel matrix of L1. Owing to their quantum-size effects and large surface-to-volume ratio, MNPs are promising materials for catalysis.69 Although access to MNPs is usually through reduction of a target metal salt with the help of external reducing agent, supramolecular gels wherein the gelator molecules have amide/urea/thiourea moieties are known to produce MNPs in situ without the help of exogenous reducing agent.70,71,72 For generating silver nanoparticles, aqueous solution of AgNO3 (2 mg in 2 mL of water) was placed over a gel bed of L1 in DMSO/H2O (3:2). The solution was kept in dark at room temperature for 24 h. The color transition was observed from white opaque gel to light-brown gel indicating the formation of Ag nanoparticles (AgNPs) which were further studied by UV-vis and TEM. A peak at  = 440 nm in the UV-vis spectrum of gel containing MNP dispersed in DMSO at room temperature was due to the characteristic surface plasmon absorption band of AgNPs. FEG-TEM images of dried gel of L1 containing AgNPs clearly showed that the MNPs were adhered to the surface of plate like gel networks. Presumably the bis-amide backbone of L1 and visible light played a crucial role in reducing Ag ion to generate AgNPs within the gel matrix (Figure 9).

both vapor and solution phase. Thus a series of CPs was achieved that displayed multi-functional properties like metallogelation and molecular iodine adsorption. The aqueous gel of L1 was also able to produce AgNPs without the help of any exogenous reducing agent. Experimental Section Materials and Methods for Physical Measurements. All reagents and chemicals are purchased from commercial sources and used without further purification. FT-IR spectra were recorded on a FTIR instrument (Perkin Elmer, FT-IR Spec-trometer, Spectrometer Two). Elemental analyses were performed on Perkin Elmer Precisely, Series-II, CHNO/S Analyser2400. TGA experiments were done on a SDT Q Series 600 Uni-versal VA.2E TA instrument. X-ray powder diffraction patterns were recorded on a Bruker AXS D8 Advance Powder (CuK radi-ation, λ = 1.5418 Å) X-ray diffractometer. TEM images were rec-orded using a JEOL instrument (JEM-2100F; JEM-2010) with 300 mesh copper TEM grid. UV/Vis spectroscopic measurements were performed on a Hewlett–Packard 8453 diode array spectro-photometer equipped with a Peltier temperature controller. NMR spectra were carried out using 400/500 MHz spectrometer (Bruker Ultrasheild Plus- 400/500). Synthesis of L1. Nicotinoyl Chloride hydrochloride (1.78 g, 10 mmol) and dry triethyl amine (1.5 mL) were dissolved in dry DCM (250 mL) in a round bottom flask (500 mL). Then 4,4'-methylenedianiline (1 g, 5 mmol) in dry DCM (5 mL) were added drop wise under nitrogen atmosphere and the reaction mixture was stirred for 12 h at reflux temperature. Obtained precipitate was filtered and washed several times with dry DCM. The ligand L2 was isolated (Yield 67%) as white precipitate followed by drying in vacuum.

Figure 9. (clockwise) Synthesis of AgNPs in gel matrix of L1; TEM images of AgNPs adhered to the gel network; EDX displaying existence of Ag; typical surface plasmon spectra of AgNPs.

teristic spectros showed surface range nm. ay, isolated Presumabl UV/Vis copy the AgNPs band absorption plasmon ntence metallogel confirmed which HRTEM, fibers were amide in backbone ligand Iienergy 0N Ag intensity color hanced and within The network. moiety reduced of remarkabl was time sthat adhered increasing 485 further AgNP ydistributio concentrat temperatur DMSO room ns e. exisby ion emetal nto was silver Ps. enhnd The tthe ctof gel Ag ohe over ad the nm he size light harac The of at the of f2–9 salt of gel the by tat lin ito= h

Conclusions. The results presented herein clearly emphasized the importance of structural rationale based on which the CPs were designed. All the CPs (CP1A-CP5) were LOCS and the corresponding reactants under suitable conditions produced metallogels (MG1, MG2, MG4 and MG5) as envisaged. One of the CPs namely CP5 displayed the ability to adsorb and release I2 from

L1: 1H NMR (500 MHz, DMSO) δ 10.39 (s, 1H), 9.09 (s, 1H), 8.75 (d, J = 5 Hz, 1H), 8.28 (d, J = 5 Hz, 1H), 7.69 (d, J = 10 Hz, 1H), 7.56 (dd, J = 10, 5 Hz, 1H), 7.23 (d, J = 10 Hz, 1H), 3.91 (s, 2H) (see supporting information Figure S1); 13C NMR (100 MHz, DMSO) δ 163.87, 152.02, 148.59, 137.11, 136.79, 135.34, 130.59, 129.07, 128.85, 123.48, 120.53 (see supporting information Figure S1). ESI-MS-(MeOH): calculated for [M+H]+ is 409.16, found 409.08 (see supporting information Figure S3). FT-IR (𝜐,cm-1): 3347, 1662, 1645, 1598, 1525, 1511, 1407, 1287, 1267, 820, 740, 706, 688, 511 (see the Supporting Information, Figure S4).

Synthesis of the Coordination Polymers. [{Cd(µ-L1)(µ-TA)(H2O)2} ・ 3H2O·MeOH]∞ (CP1A): A mixture of L1 (20 mg, 0.05 mmol) and disodium terephthalate (Na2TA; 10 mg, 0.05 mmol) in DMF (2 mL) and MeOH (2 mL) was added to an aqueous solution (1 mL) of Cd(NO3)2·4H2O ( 15 mg, 0.05 mmol) in screw capped plastic vial (25 mL) and heated at 80˚C for 48 h in an oven. The mixture was slowly cooled to rt. and



colorless block-shaped crystals were formed, which were filtered and dried in air. FT-IR (𝜐, cm-1): 3270, 1658, 1604, 1538, 1505, 1410, 1376, 1325, 1047, 827, 753, 509. [{Cd(µ-L1)( µ-TA)(H2O)} ·MeOH] ∞ (CP1B): A mixture of L1 (20 mg, 0.05 mmol) and disodium terephthalate (Na2TA; 10 mg, 0.05 mmol) in DMF (1 mL) and MeOH (2 mL) was added to an aqueous solution (3 mL) of Cd(NO3)2·4H2O (15 mg, 0.05 mmol) in screw capped plastic vial (25mL) and heated at 80˚C for 48 h in an oven. The mixture was slowly cooled to rt. and colorless blockshaped crystals were formed, which were filtered and dried in air. FT-IR (𝝊, cm-1): 3292, 1662, 1608, 1544, 1506, 1410, 1385, 1328, 1051, 823, 775, 754, 513. [{Ni(µ-L1)( µ-TA)(H2O)2} .3H2O·MeOH]∞ (CP2A): CP2A was synthesized by following the procedure used for synthesizing CP1A; in this case, Ni(NO3)2·6H2O (14.5 mg, 0.05 mmol) was used. Upon slow cooling to rt., green block shape crystals were formed, which were filtered and dried in open air. FT-IR (𝝊, cm-1): 3304, 1673, 1603, 1541, 1510, 1482, 1377, 1326, 1017, 752, 696, 597, 507). [{Ni(µ-L1)( µ-TA)(H2O)2} .4H2O·MeOH]∞ (CP2B): CP2B was synthesized by following the procedure used for synthesizing CP1B; in this case Ni(NO3)2·6H2O (14.5 mg, 0.05 mmol) was used. Upon slow cooling to rt., green block shape crystals were formed, which were filtered, washed with MeOH and dried in open air. FT-IR (𝝊, cm1):3300, 1657, 1603, 1548, 1502, 1377, 1323, 1035, 832, 753, 505. [{Cu(µ-L1)( µ-TA)(H2O)2} .3H2O]∞ (CP3). CP3 was synthesized by following the procedure used for synthesizing CP1A; in this case Cu(NO3)2·3H2O (12 mg, 0.05 mmol) was used . Upon slow cooling to rt., blue colored block shape crystals were formed, which were filtered and washed with MeOH and dried in open air. FT-IR (𝜐, cm-1): 3389, 1661, 1604, 1543, 1505, 1410, 1367, 1327, 1056, 826, 776, 751, 512. [{Zn(µ-L1)( µ-TA)(H2O)2} .3H2O·MeOH]∞ (CP4). CP4 was synthesized by following the procedure used for synthesizing CP1A; in this case Zn(NO3)2·6H2O (15 mg, 0.05 mmol) was used. Upon slow cooling to rt., colorless block shape crystals were formed, which were filtered and washed with MeOH and dried in open air. FT-IR (𝝊, cm1): 3313, 1664, 1609, 1505, 1374, 1330, 1198, 824, 755, 642, 511. [{Co(µ-L1)(µ-TA)(MeOH)(H2O)} .H2O·MeOH]∞ (CP5). CP5 was synthesized by following the procedure used for synthesizing CP1A; in this case Co(NO3)2·6H2O (14.5 mg, 0.05 mmol) was used. Upon slow cooling to rt., pink colored block shape crystals were formed, which were filtered and washed with MeOH and dried in open air. FT-IR (𝝊, cm-1):3283, 1660, 1605, 1542, 1503, 1383, 1326, 1275, 1048, 751, 512. Gelation. L1 (40 mg) was dissolved in DMSO (0.6 mL) in a glass vial (3 mL) by heating on a hot plate. The solution was cooled to rt. to which water (0.4 mL) was added resulting in instant gelation (MGC 4 wt %) as evident from tube inversion and rheological data. It was found to be thermoreversible over a few cycles.

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Metallogelation. A clear solution of L1 in DMF was mixed with an aqueous solution containing Na2TA and the corresponding metal salt in a sonicator (5-10 mins) at ambient condition that resulted in metallogel. Transmission electron Microscopy. Small amount of gel sample was smeared on a 300 mesh Cu grid and dried under vacuum at room temperature for 1 day. TEM images were recorded without staining. Single Crystal X-ray Crystallography. Single crystal X-ray data were collected by using Mokα (λ=0.7107Å) radiation on a BRUKER APEX II diffractometer equipped with CCD area detector. Data collection and data reduction were done using APEX II package software. The structures were solved by using direct methods and refined in a routine manner. Data of CP2A and CP3 were collected in Bruker D8VENTURE Micro focus diffractometer equipped with PHOTON II detector (Mo kα (λ=0.7107Å). Data collection and data reduction were done by using APEX3 software package in a routine manner. Final refinement and CIF finalization were carried out by using OLEX2 version 1.2.9. In all cases, the non-hydrogen atoms were treated anisotropically whereas most of the hydrogen atoms were geometrically fixed; wherever possible, the hydrogen atoms associated with guest solvent molecules were located on difference Fourier map and refined. CIFs files has been deposited to The Cambridge Crystallographic Data Centre (CCDC). CCDC 1863205-1863211 contain the supple-mentary crystallographic data for this paper. These data can be obtained free of charge from CCDC. Powder X-ray Diffraction. A thin layer made on a glass slide from bulk powdered sample (~15 mg) was used for data collection using Bruker AXS D8 Advanced powder diffractometer (Cukα radiation, λ=1.5406Å) equipped with super speed LYNXEXE detector with a scan speed 0.3 sec/step for scan range of 2(5˚-35˚).

ASSOCIATED CONTENT Supporting Information. Supporting information is available free of charge via the Internet at http://pubs.acs.org. 1H, 13C NMR, FT-IR, HRMS, ORTEP plots, hydrogen bonding table, TGA, PXRD patterns, Rheological data, UV-vis spectra. Author information

Corresponding author *E-mail: [email protected] ACKNOWLEDGMENT SM thanks UGC for research fellowship. P.D. thanks DST (Grant No. EMR/2016/000894) for financial support. P.D. indebted to Professor Israel Goldberg for giving him opportunity to work as a post-doctoral fellow under his supervision during the year 1994-1996. REFERENCES


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Page 10 of 12

Table 1. Crystallographic data and structure-refinement parameters for polymers CP1A–CP5. Identification code

CP1A

CP1B

CP2A

CP2B

CP3

CP4

CP5

CCDC

1863206

1863211

1863210

1863205

1863207

1863208

1863209

Empirical formula

C33.5H26CdN4O11.25 C34H30CdN4O8 C34H30N4NiO11 C34H24N4NiO13 C33H28CuN4O11

C33.25H28N4O11.5Zn C35H30CoN4O10

Formula weight

776.98

735.02

729.33

755.28

720.13

732.96

725.56

Temperature/K

296.15

296.15

142.81

100.01

298

298

120.22

Crystal system

triclinic

orthorhombic

monoclinic

triclinic

triclinic

triclinic

triclinic

Space group

P-1

Pbca

C2/c

P-1

P-1

P-1

P-1

a/Å

9.539(6)

11.4197(15)

18.505(8)

9.2545(10)

9.2658(8)

9.389(6)

9.3588(4)

b/Å

11.408(7)

20.410(3)

18.012(8)

11.1448(12)

11.0361(9)

11.324(7)

11.2448(5)

c/Å

17.330(11)

26.422(4)

21.407(9)

17.409(2)

17.4680(13)

17.511(11)

17.4321(7)

α/°

85.615(10)

90

90

92.728(4)

92.978(3)

92.451(9)

91.987(3)

β/°

85.125(10)

90

111.239(6)

90.397(4)

90.487(3)

90.647(9)

90.278(3)

γ/°

66.829(9)

90

90

113.308(4)

114.101(2)

113.400(9)

113.882(3)

Volume/Å3

1725.5(19)

6158.3(14)

6651(5)

1646.5(3)

1627.5(2)

1706.4(19)

1676.08(13)

Z

2

8

8

2

2

2

2

1.495

1.586

1.457

1.523

1.47

1.427

1.438

μ/mm-1

0.698

0.77

0.651

0.665

0.739

0.787

0.577

F(000)

786

2992

3024

776

742

755

750

Crystal size/mm3

0.36 × 0.15 × 0.1

0.3 × 0.21 × 0.28 × 0.16 × 0.31 × 0.22 × 0.9 × 0.32 × 0.2 0.12 0.12 0.15

0.25 × 0.12 × 0.08

0.34 × 0.25 × 0.18

Radiation

MoKα 0.71073)

ρcalc

g/cm3

(λ

2Θ range for data 2.362 to 40.364 collection/°

= MoKα (λ 0.71073)

= MoKα (λ 0.71073)

= MoKα (λ 0.71073)

3.082 to 53.632 3.27 to 51.12

4.512 46.848

= MoKα (λ 0.71073)

= MoKα 0.71073)

to 4.552 to 54.598

(λ

2.328 to 39.356

= MoKα (λ 0.71073)

=

3.964 to 52.812

Index ranges

-9 ≤ h ≤ 9, -11 ≤ k -14 ≤ h ≤ 14, - -22 ≤ h ≤ 22, - -10 ≤ h ≤ 9, -11 -11 ≤ h ≤ 11, -14 -8 ≤ h ≤ 8, -10 ≤ k -11 ≤ h ≤ 11, -13 ≤ ≤ 11, -16 ≤ l ≤ 16 25 ≤ k ≤ 25, -32 21 ≤ k ≤ 21, -25 ≤ k ≤ 12, -19 ≤ l ≤ k ≤ 14, -20 ≤ l ≤ 10, -16 ≤ l ≤ 16 k ≤ 14, -21 ≤ l ≤ ≤ l ≤ 33 ≤ l ≤ 25 ≤ 19 ≤ 22 21

Reflections collected

26304

Independent reflections

3297 0.0958, 0.0508]

75322 [Rint = 6523 [Rint = Rsigma = 0.0576, Rsigma = 0.0354]

80080

14161

20088

15266

6210 [Rint = 0.0923, Rsigma = 0.0446]

4759 [Rint = 7271 [Rint = 3009 0.0569, 0.0868, Rsigma = 0.0693, Rsigma = 0.1237] 0.0514] 0.0696]

21989 [Rint = 6808 [Rint = Rsigma = 0.0869, Rsigma = 0.1142]

Data/restraints/pa 3297/0/448 rameters

6523/0/427

6210/0/461

4759/0/459

7271/0/443

3009/0/449

6808/4/446

Goodness-of-fit on 1.082 F2

0.936

1.024

1.129

1.067

1.053

0.988

Final R indexes R1 = 0.0545, wR2 = R1 = 0.0436, R1 = 0.0444, R1 = 0.0916, R1 = 0.0898, R1 = 0.0650, R1 = 0.0685, [I>=2σ (I)] 0.1523 wR2 = 0.2087 wR2 = 0.1165 wR2 = 0.2384 wR2 = 0.2220 wR2 = 0.2071 wR2 = 0.1757 Final R indexes R1 = 0.0726, wR2 = R1 = 0.0722, R1 = 0.0800, R1 = 0.1157, R1 = 0.1570, R1 = 0.0850, R1 = 0.1229, [all data] 0.1684 wR2 = 0.2294 wR2 = 0.1409 wR2 = 0.2535 wR2 = 0.2666 wR2 = 0.2283 wR2 = 0.2097


10

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Table 2. Gelation and Rheology table of various metallogels. Gel

Metal Salt

Ligand (L1)

Co-Ligand (TA)

MGC (wt%)

Critical Strain (%)

G'

G"/G'

MG1

Cd(NO3)2;

6 mg

3 mg

5.4

7.74

2.37*105

0.24

4.5 mg (0.014mmol)

(0.014mmol)

(0.014mmol)

Ni(NO3)2 ;

3 mg

5.3

70.08

9.32*104

0.23

4.27 mg (0.014mmol)

6mg (0.014mmol)

Zn(NO3)2 ;

6 mg

3 mg

5.36

8.73

7.69*104

0.39

4.4 mg (0.014mmol)

(0.014mmol)

(0.014mmol)

Co(NO3)2;

6 mg

3 mg

5.31

7.01

2.03*103

0.42

4.28 mg (0.014mmol)

(0.014mmol)

(0.014mmol)

MG2 MG4 MG5

(0.014mmol)


11


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SYNOPSIS TOC. A crystal engineering based approach has been adopted to generate a series of coordination polymers that displayed both metallogelation and I2 adsorption

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12

Mixed Ligand Coordination Polymers for Metallogelation and Iodine

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